Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 781 - 788 (1984)
Update date:2022-08-11
Topics:
Cox, Brian G.
Jedral, Wojciech
The application of square-wave amperometry, an analytical technique involving the use of two indicator electrodes polarized by a square wave, in the determination of reaction rates is described.Kinetic measurements have been made on the bromination of anisole in aqueous solution.Square-wave amperometry in conjunction with a stopped-flow apparatus equipped with Pt electrodes in the observation tube was used to monitor the disappearance of bromine in dilute solutions.Reaction rates with half-lives down to ca. 5 ms can be measured using relatively high-frequency square waves (ca. 800-1000 Hz).The results are in good agreement with values measured spectrophotometrically at higher bromine concentrations.The rate of dissociation of Ag(1+) from its macrobicyclic cryptand 211 complex was also measured, using a pair of silver indicator electrodes.Free Ag(1+) may be monitored selectively in the presence of its cryptate complex by using a low-amplitude square wave (+/- 150 mV).The advantages and limitations of the amperometric technique for kinetic measurements are discussed.
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